EP3923380A1 - Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé - Google Patents

Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé Download PDF

Info

Publication number
EP3923380A1
EP3923380A1 EP21177241.3A EP21177241A EP3923380A1 EP 3923380 A1 EP3923380 A1 EP 3923380A1 EP 21177241 A EP21177241 A EP 21177241A EP 3923380 A1 EP3923380 A1 EP 3923380A1
Authority
EP
European Patent Office
Prior art keywords
metal oxide
composite
active material
cathode active
composite cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP21177241.3A
Other languages
German (de)
English (en)
Other versions
EP3923380B1 (fr
Inventor
Inhyuk Son
Sangkook Mah
SungNim JO
Andrei Kapylou
Guesung Kim
Jongseok Moon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung SDI Co Ltd
Original Assignee
Samsung SDI Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Publication of EP3923380A1 publication Critical patent/EP3923380A1/fr
Application granted granted Critical
Publication of EP3923380B1 publication Critical patent/EP3923380B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • One or more aspects of embodiments of the present disclosure relate to a composite cathode active material, a cathode including the composite cathode active material, a lithium battery employing the cathode, and a method of preparing the composite cathode active material.
  • lithium batteries In order to meet the desired miniaturization and high performance of various devices, in addition to miniaturization and weight reduction of lithium batteries, high energy density of lithium batteries is becoming more important. Among other things, high-capacity lithium batteries are becoming more important.
  • Nickel-based cathode active materials in the art have poor lifetime characteristics and poor thermal stability due to side reactions.
  • One or more aspects of embodiments of the present disclosure are directed toward a novel composite cathode active material capable of preventing or reducing the deterioration of battery performance by suppressing or reducing the side reactions of the composite cathode active material.
  • One or more aspects of embodiments of the present disclosure are directed toward a cathode including the composite cathode active material.
  • One or more aspects of embodiments of the present disclosure are directed toward a lithium battery employing the cathode.
  • One or more aspects of embodiments of the present disclosure are directed toward a method of preparing the composite cathode active material.
  • a composite cathode active material includes:
  • a cathode includes the composite cathode active material.
  • a lithium battery includes the cathode.
  • a method of preparing a composite cathode active material includes:
  • spatially relative terms such as “beneath,” “below ,” “lower,” “above,” “upper,” “bottom,” “top” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” or “over” the other elements or features. Thus, the term “below” may encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein should be interpreted accordingly.
  • the terms “substantially”, “about”, and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.
  • “About” or “approximately,” as used herein, is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ⁇ 30%, 20%, 10%, 5% of the stated value.
  • any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range.
  • a range of "1.0 to 10.0" is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6.
  • Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
  • a composite cathode active material according to embodiments, a cathode including the composite cathode active material, a lithium battery including the cathode, and a method of preparing the composite cathode active material will be described in more detail.
  • a composite cathode active material includes: a core including a lithium transition metal oxide; and a shell disposed (e.g., positioned) on and conforming to a surface of the core, wherein the shell includes at least one first metal oxide represented by Formula M a O b (0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 4, when a is 1, 2, or 3, b is not an integer), and carbonaceous material, the first metal oxide is placed in a carbonaceous material matrix, M is at least one metal selected from groups 2 to 13, group 15, and group 16 of the Periodic Table of Elements, the lithium transition metal oxide contains nickel, and the content of nickel is 80 mol% or more based on the total moles of transition metal.
  • the total moles of transition metals means the total moles of elements other than lithium and oxygen (and, if present, F, S, Br and CI) in the lithium transition metal oxide.
  • a shell including a first metal oxide and carbonaceous material is disposed on and/or conformed to a core of the composite cathode active material.
  • Uniform (e.g., substantially uniform) coating of related art carbonaceous material on the core is difficult to attain due to aggregation (e.g., aggregation of particles comprising the shell).
  • the composite cathode active material of the present embodiments uses a composite including at least one first metal oxide or a plurality of first metal oxides disposed within a carbonaceous material matrix, thereby preventing or reducing the aggregation of carbonaceous material and placing a uniform (e.g., substantially uniform) shell on the core.
  • a contact between a core and an electrolyte may be effectively blocked or reduced, thereby preventing or reducing the side reactions that may occur due to the contact between the core and the electrolyte.
  • reduction (Ni 3+ ->Ni 2+ ) of nickel ions due to the electrolyte and the mixing of cations due to the electrolyte may be suppressed or reduced, thereby preventing or reducing the formation of a resistance layer such as a NiO phase.
  • elution of nickel ions may also be suppressed or reduced.
  • the carbonaceous material may be for example a crystalline carbonaceous material.
  • the carbonaceous material may be a carbonaceous nanostructure.
  • the carbonaceous material may be a graphene.
  • the shell including carbonaceous material e.g . graphene
  • the shell including carbonaceous material has flexibility
  • a change in volume of the composite cathode active material may be easily (or suitably) accepted during charging and discharging of the battery, and occurrence of cracks in the composite cathode active material may be suppressed or reduced.
  • carbonaceous material e.g . graphene
  • has high electronic conductivity interfacial resistance between the composite cathode active material and the electrolyte decreases. Therefore, despite the introduction of a shell containing carbonaceous material (e.g . graphene), internal resistance of a lithium battery is maintained or reduced.
  • the shell may include, for example, one kind of first metal oxide or two or more kinds of different first metal oxides.
  • the lithium transition metal oxide has a nickel content of 80 mol% or more based on the total moles of transition metal(s), and the shell including the first metal oxide and carbonaceous material is disposed on the core, thereby simultaneously (or concurrently) providing high discharge capacity and improved cycle characteristics. Accordingly, the composite cathode active material having a nickel content of 80 mol% or more may provide improved capacity and excellent lifetime characteristics as compared with a composite cathode active material having a relatively low nickel content.
  • the metal included in the first metal oxide may be at least one selected from Al, Nb, Mg, Sc, Ti, Zr, V, W, Mn, Fe, Co, Pd, Cu, Ag, Zn, Sb, and Se.
  • the first metal oxide may be, for example, at least one selected from Al 2 O z (0 ⁇ z ⁇ 3), NbO x (0 ⁇ x ⁇ 2.5), MgO x (0 ⁇ x ⁇ 1), Sc 2 O z (0 ⁇ z ⁇ 3), TiO y (0 ⁇ y ⁇ 2), ZrO y (0 ⁇ y ⁇ 2), V 2 O z (0 ⁇ z ⁇ 3), WO y (0 ⁇ y ⁇ 2), MnO y (0 ⁇ y ⁇ 2), Fe 2 O z (0 ⁇ z ⁇ 3), Co 3 O w (0 ⁇ w ⁇ 4), PdO x (0 ⁇ x ⁇ 1), CuO x (0 ⁇ x ⁇ 1), AgO x (0 ⁇ x ⁇ 1), ZnO x (0 ⁇ x ⁇ 1), Sb 2 O z (0 ⁇ z ⁇ 3), and SeO y (0 ⁇
  • the shell includes Al 2 O x (0 ⁇ x ⁇ 3) as the first metal oxide.
  • the shell may further include at least one kind of second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer).
  • M is at least one metal selected from groups 2 to 13, group 15, and group 16 of the Periodic Table of Elements.
  • the second metal oxide includes the same metal as the first metal oxide, and the ratio c/a of c to a in the second metal oxide is greater than the ratio b/a of b to a in the first metal oxide. For example, c/a >b/a.
  • the second metal oxide is selected from Al 2 O 3 , NbO, NbO 2 , Nb 2 O 5 MgO, SC 2 O 3 , TiO 2 , ZrO 2 , V 2 O 3 , WO 2 , MnO 2 , Fe 2 O 3 , Co 3 O 4 , PdO, CuO, AgO, ZnO, Sb 2 O 3 , and SeO 2 .
  • the first metal oxide is a reduction product of the second metal oxide.
  • the first metal oxide is obtained by reducing a part or all of the second metal oxide. Accordingly, the first metal oxide has a lower oxygen content and a lower metal oxidation number than the second metal oxide.
  • the shell includes Al 2 O x (0 ⁇ x ⁇ 3) as the first metal oxide and Al 2 O 3 as the second metal oxide.
  • the carbonaceous material included in the shell is chemically bonded to the transition metal of the lithium transition metal oxide included in the core through a chemical bond.
  • a carbon atom (C) of the carbonaceous material in the shell is chemically bonded to a transition metal (Me) of the lithium transition metal oxide (using an oxygen atom as an intermediate) through C-O-Me bonding (for example, C-O-Ni bonding).
  • the carbonaceous material included in the shell is chemically bonded to the lithium transition metal oxide included in the core to allow the core and the shell to be a composite. Therefore, the composite of the core and the shell is distinguished from a simple physical mixture of carbonaceous material and lithium transition metal oxide.
  • the first metal oxide and carbonaceous material included in the shell are chemically bonded through a chemical bond.
  • the chemical bond is covalent bonding or ionic bonding.
  • the covalent bond is, for example, a bond including at least one selected from an ester group, an ether group, a carbonyl group, an amide group, a carbonate anhydride group, and an acid anhydride group.
  • the ionic bond is, for example, a bond including a carboxylic acid ion, an ammonium ion, and/or an acyl cation group.
  • the thickness of the shell is, for example, about 1 nm to about 5 ⁇ m, about 1 nm to about 1 ⁇ m, about 1 nm to about 500 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 90 nm, about 1 nm to about 80 nm, about 1 nm to about 70 nm, about 1 nm to about 60 nm, about 1 nm to about 50 nm, about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 20 nm, or about 1 nm to about 10 nm.
  • an increase in internal resistance of a lithium battery including the composite cathode active material is suppressed or reduced.
  • the composite cathode active material may further include: a third metal doped on the core; or a third metal oxide applied on the core.
  • the shell may be disposed (e.g., provided) on the doped third metal or the applied third metal oxide.
  • the shell may be placed on the third metal and/or the third metal oxide.
  • the composite cathode active material may include a core; an intermediate layer disposed on the core; and a shell disposed on the intermediate layer, wherein the intermediate layer may include a third metal or a third metal oxide.
  • the third metal may be at least one metal selected from Al, Zr, W, and Co, and the third metal oxide may be Al 2 O 3 , Li 2 O-ZrO 2 , WO 2 , CoO, Co 2 O 3 , Co 3 O 4 , and/or the like.
  • the shell included in the composite cathode active material includes at least one selected from a composite including the first metal oxide and the carbonaceous material (for example, graphene) and a resulting product of milling of the composite, and the first metal oxide is placed in a carbonaceous material matrix, for example, graphene matrix.
  • the shell is prepared from a composite including the first metal oxide and the carbonaceous material.
  • the composite may further include a second metal oxide in addition to the first metal oxide.
  • the composite may include, for example, two or more kinds of first metal oxides.
  • the composite may include, for example, two or more kinds of first metal oxides and two or more kinds of second metal oxides.
  • the content of the composite in the composite cathode active material may be about 3wt% or less, about 2wt% or less, about 1wt% or less, about 0.5wt% or less, or about 0.2wt% or less, based on the total weight of the composite cathode active material.
  • the content of the composite may be about 0.01wt% to about 3wt%, about 0.01wt% to about 1wt%, about 0.01wt% to about 0.7wt%, about 0.01wt% to about 0.6wt%, about 0.1 wt% to about 0.5wt%, about 0.01wt% to about 0.2wt%, about 0.01wt% to about 0.1wt%, or about 0.03wt% to about 0.07wt%, based on the total weight of the composite cathode active material.
  • the composite cathode active material includes the composite within any of these ranges, the cycle characteristics of the lithium battery including the composite cathode active material are further improved.
  • At least one selected from the first metal oxide and second metal oxide included in the composite may has an average particle diameter of about 1 nm to about 1 ⁇ m, about 1 nm to about 500 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 70 nm, about 1 nm to about 50 nm, about 1 nm to about 30 nm, about 3 nm to about 30 nm, about 3 nm to about 25 nm, about 5 nm to about 25 nm, about 5 nm to about 20 nm, or about 7 nm to about 20 nm.
  • the first metal oxide and/or the second metal oxide may be more uniformly distributed in the carbonaceous material matrix (for example, a graphene matrix) of the composite because the first metal oxide and/or the second metal oxide has a particle diameter within any of these nanometer ranges. Therefore, such a composite may be uniformly (e.g., substantially uniformly) applied on the core to form a shell. Further, the first metal oxide and/or the second metal oxide may be more evenly disposed (e.g., distributed) on the core because the first metal oxide and/or the second metal oxide has a particle diameter within any of the above nanometer ranges. Therefore, the first metal oxide and/or the second metal oxide may be uniformly (e.g., substantially uniformly) disposed on the core, thereby more effectively exhibiting voltage resistance characteristics.
  • the carbonaceous material matrix for example, a graphene matrix
  • the average particle diameter of the first metal oxide and the second metal oxide is measured by a measurement apparatus using a laser diffraction method and/or a dynamic light scattering method.
  • the average particle diameter of the first metal oxide and the second metal oxide may be measured using a laser scattering particle size distribution meter (for example, LA-920 of Horiba Ltd.), and is a value of the median diameter (D50) when the metal oxide particles are accumulated to 50 % from small particles in volume conversion.
  • the uniformity deviation of at least one selected from the first metal oxide and second metal oxide included in the composite may be about 3 % or less, about 2 % or less, or about 1 % or less.
  • the uniformity may be obtained, for example, by X-ray photoelectron spectroscopy (XPS). Accordingly, at least one selected from the first metal oxide and second metal oxide included in the composite may have a uniformity deviation of about 3 % or less, about 2 % or less, or about 1 % or less, and may be uniformly (e.g., substantially uniformly) distributed.
  • the carbonaceous material included in the composite may have a branched structure, and at least one selected from the first metal oxide and the second metal oxide may be distributed in the branched structure of the carbonaceous material.
  • the branched structure of the carbonaceous material includes a plurality of carbonaceous material particles contacting each other. Since the carbonaceous material has a branched structure, various conductive paths may be provided.
  • the carbonaceous material included in the composite may be or have a graphene.
  • the branched structure of the graphene includes a plurality of graphene particles contacting each other. Because the graphene has a branched structure, various conductive paths may be provided.
  • the carbonaceous material included in the composite may have a spherical structure, and at least one selected from the first metal oxide and the second metal oxide may be distributed in the spherical structure.
  • the spherical structure of the carbonaceous material may have a size of about 50 nm to 300 nm.
  • a plurality of carbonaceous materials having a spherical structure may be provided. Since the carbonaceous material has a spherical structure, the composite may have a robust structure.
  • the carbonaceous material included in the composite may be or include a graphene.
  • the spherical structure of the graphene may have a size of about 50 nm to about 300 nm.
  • a plurality of graphenes having a spherical structure may be provided. Because the graphene has a spherical structure, the composite may have a robust structure.
  • the carbonaceous material included in the composite may have a spiral structure in which the plurality of spherical structures are connected to each other, and at least one selected from the first metal oxide and the second metal oxide may be distributed in the spherical structures of the spiral structure.
  • the spiral structure of the carbonaceous material may have a size of about 500 nm to 100 ⁇ m. Since the carbonaceous material has a spiral structure, the composite may have a robust structure.
  • the carbonaceous material included in the composite may be or include a graphene.
  • the spiral structure of the graphene may have a size of about 500 nm to about 100 ⁇ m. Because the graphene has a spiral structure, the composite may have a robust structure.
  • the carbonaceous material included in the composite may have a cluster structure in which the plurality of spherical structures are aggregated with each other, and at least one selected from the first metal oxide and the second metal oxide may be distributed in the spherical structures of the cluster structure.
  • the cluster structure of the carbonaceous material may have a size of about 5 ⁇ m to about 1 mm or about 0.5 mm to 10 cm. Since the carbonaceous material has a cluster structure, the composite may have a robust structure.
  • the carbonaceous material included in the composite may be or include a graphene.
  • the cluster structure of the graphene may have a size of about 5 ⁇ m to 1 mm or about 0.5 mm to about 10 cm.
  • the composite may have a robust structure.
  • the size of the spherical structure, the spiral structure, or the cluster structure may be measured by Scanning Electron Microscope (SEM) or Transmission Electron Microscopy (TEM).
  • SEM Scanning Electron Microscope
  • TEM Transmission Electron Microscopy
  • the size of the spherical structure, the spiral structure, or the cluster structure may be an average diameter of the structures.
  • the composite may be a crumpled faceted-ball structure, and at least one selected from the first metal oxide and the second metal oxide may be distributed inside the structure or on the surface of the structure.
  • the composite may be easily applied on the irregular surface irregularities of the core.
  • the composite may be a planar structure, and at least one selected from the first metal oxide and the second metal oxide may be distributed inside the structure or on the surface of the structure.
  • the composite may be easily applied on the irregular surface irregularities of the core.
  • the carbonaceous material included in the composite may extend from the first metal oxide by a distance of about 10 nm or less, and may include at least 1 to 20 carbonaceous material layers. For example, since a plurality of carbonaceous material layers are laminated, carbonaceous material having a total thickness of 12 nm or less may be placed on the first metal oxide. For example, the total thickness of the carbonaceous material may be about 0.6 nm to about 12 nm.
  • the carbonaceous material included in the composite may be or include a graphene. For example, because a plurality of graphene layers ( e.g . at least 1 to 20 graphene layers) are laminated, graphene ( e.g .
  • the total thickness of the graphene (e.g . at least 1 to 20 graphene) may be about 0.6 nm to about 12 nm.
  • the core included in the composite cathode active material includes, for example, a lithium transition metal oxide represented by Formula 1 below: Formula 1 LiaNi x CoyM z O 2-b A b .
  • M is at least on selected from manganese (Mn), niobium (Nb), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr)), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), and boron (B), and A is F, S, CI, Br, or a combination thereof.
  • the core included in the composite cathode active material includes, for example, a lithium transition metal oxide represented by any one of Formulae 2 and 3 below: Formula 2 LiNi x Co y Mn z O 2 Formula 3 LiNi x Co y Al z O 2 .
  • Each of the lithium transition metal oxides of Formulae 1 to 3 has a relatively high nickel content of about 80mol% or more, about 85mol% or more, or about 90mol% or more based on the total moles of transition metals (e.g . based on 100mol% of the total amount of Ni, Co and M for Formula 1, based on 100mol% of the total amount of Ni, Co and Mn for Formula 2, and based on 100mol% of the total amount of Ni, Co and Al for Formula 3), and may provide excellent (or improved) initial capacity, roomtemperature lifetime characteristics and high-temperature lifetime characteristics.
  • a cathode according to one or more embodiments includes the above-described composite cathode active material. Because the cathode includes the above-described composite cathode active material, the cathode provides improved cycle characteristics and thermal stability.
  • the cathode may be manufactured by the following method, but the manufacturing method thereof is not necessarily limited to the exemplified method and may be adjusted according to required conditions.
  • a cathode active material composition is prepared by mixing the above-described composite cathode active material, a conductive agent, a binder, and a solvent.
  • the prepared cathode active material composition is directly applied and dried on an aluminum current collector to form a cathode plate provided with a cathode active material layer.
  • a film obtained by casting the cathode active material composition on a separate support and then separating the composition from the support is laminated on the aluminum current collector to form a cathode plate provided with a cathode active material layer.
  • conductive agent carbon black, graphite fine particles, natural graphite, artificial graphite, acetylene black, Ketjen black, carbon fiber; carbon nanotubes; metal powder, metal fiber and/or metal tube such as copper, nickel, aluminum, and/or silver; and/or conductive polymers such as polyphenylene derivatives may be used, but the present disclosure is not limited thereto. Any suitable conductive agent may be used.
  • a vinylidene fluoride/hexafluoropropylene copolymer a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a mixture of the above-described polymers, and/or a styrene butadiene rubber polymer may be used, but the present disclosure is not limited thereto.
  • Any suitable binder may be used.
  • NMP N-methylpyrrolidone
  • acetone acetone
  • water any suitable solvent may be used.
  • pores in the electrode plate by further adding a plasticizer and/or a pore former to the cathode active material composition.
  • the contents (e.g., amounts) of the composite cathode active material, conductive agent, binder, and solvent used in the cathode may be at levels suitable for use in lithium batteries.
  • one or more of the conductive agent, the binder, and the solvent may be omitted.
  • the cathode may additionally include a general cathode active material other than the above-described composite cathode active material.
  • any suitable lithium-containing metal oxide may be used without limitation.
  • at least one selected from composite oxides of lithium and a metal selected from cobalt, manganese, nickel, and a combination thereof may be used as the lithium-containing metal oxide.
  • a compound represented by any one Formula selected from Li a A 1-b B b D 2 (where, 0.90 ⁇ a ⁇ 1, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B b O 2-c D c (where, 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiE 2-b B b O 4-c D c (where, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05); LiaNi 1-b-c Co b B c D ⁇ (where, 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and 0 ⁇ ⁇ ⁇ 2); LiaNi 1-b-c Co b B c O 2- ⁇ F ⁇ (where, 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, and
  • A is Ni, Co, Mn, or a combination thereof
  • B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
  • D is O, F, S, P, or a combination thereof
  • E is Co, Mn, or a combination thereof
  • F is F, S, P, or a combination thereof
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof
  • Q is Ti, Mo, Mn, or a combination thereof
  • I is Cr, V, Fe, Sc, Y, or a combination thereof
  • J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.
  • a compound in which a coating layer is provided on the surface of the above-described compound may be used, and a mixture of the above-described compound and the compound provided with the coating layer may also be used.
  • the coating layer provided on the surface of the above-described compound may include a coating element compound such as an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, and/or a hydroxycarbonate of a coating element.
  • the compound constituting this coating layer may be amorphous or crystalline.
  • the coating element included in the coating layer may be Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof.
  • the method of forming the coating layer is selected within a range that does not adversely affect the physical properties of the cathode active material.
  • the coating method is, for example, spray coating, dipping method, and/or the like. A more detailed description of the coating method will not be provided because it may be well understood by those in the art.
  • a lithium battery according to one or more embodiments employs a cathode including the above-described composite cathode active material.
  • the lithium battery employs a cathode including the above-described composite cathode active material, improved cycle characteristics and thermal stability are provided.
  • the lithium battery may be manufactured, for example, by the following method, but the present disclosure is not necessarily limited to the exemplified method and may be adjusted according to required conditions.
  • a cathode is prepared according to the above-described method of preparing a cathode.
  • an anode is prepared as follows.
  • the anode is prepared in substantially the same manner as the cathode, except that an anode active material is used instead of the composite cathode active material.
  • an anode active material composition a conductive agent, a binder, and a solvent, which are substantially the same as those in the cathode, may be used.
  • an anode active material, a conductive agent, a binder, and a solvent are mixed to prepare an anode active material composition, and this anode active material composition is directly applied onto a copper current collector to prepare an anode plate.
  • a film obtained by casting the prepared anode active material composition on a separate support and then separating the composition from the support is laminated on the copper current collector to prepare an anode plate.
  • the anode active material includes at least one selected from a lithium metal, a metal alloyable with lithium, a transition metal oxide, a non-transition metal oxide, and a carbon-based material.
  • Examples of the metal alloyable with lithium include Si, Sn, Al, Ge, Pb, Bi, Sb, an Si-Y alloy (Y is an alkali metal, an alkali-earth metal, a group 13 element, a group 14 element, a transition metal, an rare earth element, or a combination thereof, and Y is not Si), and an Sn-Y alloy (Y is an alkali metal, an alkali-earth metal, a group 13 element, a group 14 element, a transition metal, an rare earth element, or a combination thereof, and Y is not Sn).
  • Si-Y alloy Y is an alkali metal, an alkali-earth metal, a group 13 element, a group 14 element, a transition metal, an rare earth element, or a combination thereof, and Y is not Si
  • Sn-Y alloy Y is an alkali metal, an alkali-earth metal, a group 13 element, a group 14 element, a transition metal, an rare earth element, or a combination
  • the element Y is, for example, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.
  • the transition metal oxide is, for example, lithium titanium oxide, vanadium oxide, and/or lithium vanadium oxide.
  • the non-transition metal oxide is, for example, SnO 2 and/or SiO x (0 ⁇ x ⁇ 2).
  • the carbon-based material is, for example, crystalline carbon, amorphous carbon, or a mixture thereof.
  • the crystalline carbon is, for example, graphite such as plate-like, flake-like, spherical and/or fibrous natural graphite, and/or artificial graphite.
  • the amorphous carbon is, for example, soft carbon (low-temperature fired carbon), hard carbon, mesophase pitch carbide, and/or fired coke.
  • the contents (e.g., amounts) of the anode active material, conductive agent, binder, and solvent used in the anode may be at levels suitable for use in lithium batteries.
  • one or more of the conductive agent, the binder, and the solvent may be omitted.
  • a separator may be inserted between the cathode and the anode is prepared.
  • any separator may be used as long as it is suitable for use in lithium batteries.
  • a separator for example, a separator having low resistance to ion movement of an electrolyte and/or an excellent (or suitable) electrolyte-moisturizing ability may be used.
  • the separator may be formed of a non-woven fabric or a woven fabric including at least one selected from fiberglass, polyester, Teflon ® , polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and a combination thereof.
  • a rollable separator including polyethylene, polypropylene, and/or the like may be used, and for a lithium-ion polymer battery, a separator having excellent (or suitable) organic electrolyte impregnation ability may be used.
  • the separator may be manufactured by the following method, but the present disclosure is not necessarily limited to the exemplified method and may be adjusted according to required conditions.
  • a polymer resin, a filler, and a solvent are mixed to prepare a separator composition.
  • the separator composition is directly applied and dried on an electrode to form a separator.
  • a film obtained by casting and drying the separator composition on a support and then separating the composition from the support is laminated on the electrode to form a separator.
  • the polymer used for manufacturing the separator is not particularly limited, and any polymer may be used as long as it is suitable for use for the binder of an electrode plate.
  • a vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or a mixture thereof may be used.
  • the electrolyte is, for example, an organic electrolyte.
  • the organic electrolyte is prepared, for example, by dissolving a lithium salt in an organic solvent.
  • any suitable organic solvent may be used.
  • the organic solvent is, for example, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, ⁇ -butyrolactone, dioxolane, 4-methyldioxolane, N,N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane,1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, dimethyl ether, or a mixture thereof.
  • any suitable lithium salt may be used.
  • the lithium salt is, for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 )(here, x and y are natural numbers), LiCI, Lil, or a mixture thereof.
  • the electrolyte is a solid electrolyte.
  • the solid electrolyte is, for example, boron oxide and/or lithium oxynitride, but is not limited thereto. Any suitable solid electrolyte may be used.
  • the solid electrolyte is formed on the anode by a method such as sputtering, or a separate solid electrolyte sheet is laminated on the anode.
  • a lithium battery 1 includes a cathode 3, an anode 2, and a separator 4.
  • the cathode 3, the anode 2, and the separator 4 are wound or folded to be accommodated in a battery case 5.
  • An organic electrolyte is injected into the battery case 5, and the battery case 5 is sealed with a cap assembly 6 to complete the lithium battery 1.
  • the battery case 5 is cylindrical, but is not necessarily limited to this shape, and, for example, the shape of the battery case 5 may be a square, a thin film, and/or the like.
  • a pouch type lithium battery (e.g., a pouch lithium battery) includes at least one cell structure.
  • a separator is disposed (e.g., positioned) between a cathode and an anode to form a cell structure. After the cell structure is stacked in a bi-cell structure, it is impregnated with an organic electrolytic solution, and is accommodated and sealed in a pouch to complete the pouch lithium battery.
  • a plurality of cell structures are stacked to form a battery pack, and this battery pack may be used in devices requiring high capacity and high output.
  • the battery pack according to the present embodiments may be used in notebook computers, smart phones, electric vehicle, and/or the like.
  • the lithium battery may be used in electric vehicles (EVs).
  • the lithium battery may be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs).
  • PHEVs plug-in hybrid electric vehicles
  • the lithium battery may be used in fields (e.g., for applications) where a large amount of power storage is required.
  • the lithium battery may be used in electric bicycles, power tools, and/or the like.
  • a method of preparing a composite cathode active material includes: providing a lithium transition metal oxide; providing a composite; and mechanically milling the lithium transition metal oxide and the composite, wherein the composite includes at least one first metal oxide represented by Formula M a O b (0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 4, when a is 1, 2, or 3, b is not an integer), and carbonaceous material (e.g. graphene), the first metal oxide is disposed within a carbonaceous material matrix, M is at least one metal selected from groups 2 to 13, group 15, and group 16 of the Periodic Table of Elements, the lithium transition metal oxide contains nickel, and the content of nickel is about 80 mol% or more based on the total moles of transition metal.
  • M is at least one metal selected from groups 2 to 13, group 15, and group 16 of the Periodic Table of Elements
  • the lithium transition metal oxide contains nickel
  • the content of nickel is about 80 mol% or more based on the total moles of transition metal.
  • the lithium transition metal oxide is, for example, the above-described compound represented by any one of Formulae 1 to 3.
  • the providing the composite includes, for example, supplying a reaction gas including a carbon source gas to a structure including a metal oxide, and performing heat treatment.
  • the providing the composite includes, for example, supplying a reaction gas including a carbon source gas to a second metal oxide represented by Formula M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer) and performing heat treatment, and M is at least one metal selected from groups 2 to 13, group 15, and group 16 of the Periodic Table of Elements.
  • the carbon source gas may be a compound represented by Formula 4 below, or may be a mixed gas of the compound represented by Formula 4 and at least one selected from a compound represented by Formula 5 below and an oxygen-containing gas represented by Formula 6 below.
  • Formula 4 CnH (2n+2-a) [OH] a ,
  • n is 1 to 20 and a is 0 or 1 ;
  • Formula 5 CnH 2n ,
  • n 2 to 6; and Formula 6 C x H y O z , in Formula 6, x is an integer of 0 or 1 to 20, y is an integer of 0 or 1 to 20, and z is 1 or 2.
  • the compound represented by Formula 4 and the compound represented by Formula 5 includes at least one selected from methane, ethylene, propylene, methanol, ethanol, and propanol.
  • the oxygen-containing gas represented by Formula 6 includes carbon dioxide (CO 2 ), carbon monoxide (CO), water vapor (H 2 O), or a mixture thereof.
  • a cooling process using at least one inert gas selected from nitrogen, helium, and argon may be further performed.
  • the cooling process refers to a process of adjusting temperature to room temperature (about 20 °C to about 25 °C).
  • the carbon source gas may include at least one inert gas selected from nitrogen, helium, and argon.
  • the process of growing carbonaceous material for example graphene according to a gas phase reaction may be performed under various conditions.
  • a reactor provided with the second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer), and is heated to heat treatment temperature (T).
  • the heating time up to heat treatment temperature (T) is about 10 minutes to about 4 hours, and the heat treatment temperature (T) is about 700 °C to about 1100 °C.
  • Heat treatment is performed at the heat treatment temperature (T) for a reaction time.
  • the reaction time is, for example, about 4 hours to about 8 hours.
  • the resultant product of heat treatment is cooled to room temperature to prepare a composite.
  • the time taken to perform the process of cooling the resultant product from the heat treatment temperature to room temperature is, for example, about 1 hour to 5 hours.
  • a second condition for example, first, hydrogen is supplied to a reactor provided with the second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer), and is heated to heat treatment temperature (T).
  • the heating time up to heat treatment temperature (T) is about 10 minutes to about 4 hours, and the heat treatment temperature (T) is about 700 °C to about 1100 °C.
  • methane gas is supplied, and heat treatment is performed for residual reaction time.
  • the reaction time is, for example, about 4 hours to about 8 hours.
  • the resultant product of heat treatment is cooled to room temperature to prepare a composite.
  • nitrogen is supplied during the process of cooling the resultant product.
  • the time taken to perform the process of cooling the resultant product from the heat treatment temperature to room temperature is, for example, about 1 hour to 5 hours.
  • a reactor provided with the second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer), and is heated to heat treatment temperature (T).
  • the heating time up to heat treatment temperature (T) is about 10 minutes to about 4 hours, and the heat treatment temperature (T) is about 700 °C to about 1100 °C.
  • a mixed gas of methane and hydrogen is supplied, and heat treatment is performed for residual reaction time.
  • the reaction time is, for example, about 4 hours to about 8 hours.
  • the resultant product of heat treatment is cooled to room temperature to prepare a composite.
  • nitrogen is supplied during the process of cooling the resultant product.
  • the time taken to perform the process of cooling the resultant product from the heat treatment temperature to room temperature is, for example, about 1 hour to 5 hours.
  • the carbon source gas when the carbon source gas includes water vapor, a composite having very excellent (or improved) conductivity may be obtained.
  • the content of water vapor in the gas mixture is not limited, and is, for example, about 0.01 vol% to about 10 vol% based on 100 vol% of the total carbon source gas.
  • the carbon source gas may be, for example, methane; a mixed gas containing methane and an inert gas; or a mixed gas containing methane and an oxygen-containing gas.
  • the carbon source gas may be, for example, methane; a mixed gas of methane and carbon dioxide; or a mixed gas of methane, carbon dioxide and water vapor.
  • the molar ratio of methane and carbon dioxide in the mixed gas of methane and carbon dioxide is about 1: 0.20 to about 1:0.50, about 1: 0.25 to about 1:0.45, or about 1:0.30 to about 1: 0.40.
  • the molar ratio of methane and carbon dioxide and water vapor in the mixed gas of methane and carbon dioxide and water vapor is about 1:0.20 to 0.50: 0.01 to 1.45, about 1: 0.25 to 0.45: 0.10 to 1.35, or about 1: 0.30 to 0.40: 0.50 to 1.0.
  • the carbon source gas is, for example, carbon monoxide and/or carbon dioxide.
  • the carbon source gas is, for example, a mixed gas of methane and nitrogen.
  • the molar ratio of methane and nitrogen in the mixed gas of methane and nitrogen is about 1: 0.20 to about 1: 0.50, about 1: 0.25 to about 1: 0.45, or about 1: 0.30 to about 1: 0.40.
  • the carbon source gas may not include an inert gas such as nitrogen.
  • the heat treatment pressure may be selected in consideration of the heat treatment temperature, the composition of the gas mixture, and the desired coating amount of carbon.
  • the heat treatment pressure may be controlled by adjusting the amount of the inflowing gas mixture and the amount of the outflowing gas mixture.
  • the heat treatment pressure is, for example, about 0.5 atm or more, about 1 atm or more, about 2 atm or more, about 3 atm or more, about 4 atm or more, or about 5 atm or more.
  • the heat treatment time may be selected in consideration of the heat treatment temperature, the heat treatment pressure, the composition of the gas mixture, and the desired coating amount of carbon.
  • the reaction time at the heat treatment temperature is, for example, about 10 minutes to about 100 hours, about 30 minutes to about 90 hours, or about 50 minutes to about 40 hours.
  • the amount of carbon (e.g., graphene) deposited increases, and thus, the electrical properties of the composite may be improved.
  • the increase in the amount of deposited carbon may not necessarily be proportional to time. For example, after a set or predetermined period of time, the deposition of carbon (e.g., graphene) may no longer occur, or the deposition rate of carbon (e.g., graphene) may be lowered.
  • At least one selected from a second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer) and a reduction product thereof, which is a first metal oxide represented by M a O b (0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 4, when a is 1, 2, or 3, b is not an integer) is subjected to uniform (e.g., substantially uniform) carbonaceous material coating, for example, graphene coating, even at relatively low temperature, through the gas phase reaction of the above-described carbon source gas to obtain a composite.
  • uniform e.g., substantially uniform
  • the composite includes a carbonaceous material matrix, for example, graphene matrix having at least one structure selected from a spherical structure, a spiral structure in which a plurality of spherical structures are connected (e.g., coupled) to each other, and a cluster structure in which a plurality of spherical structures are aggregated with each other, and at least one selected from a first metal oxide represented by M a O b (0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 4, when a is 1, 2, or 3, b is not an integer) and a second metal oxide represented by M a O c (0 ⁇ a ⁇ 3, 0 ⁇ c ⁇ 4, when a is 1, 2, or 3, c is an integer) which are placed in the carbonaceous material matrix, for example, graphene matrix.
  • a carbonaceous material matrix for example, graphene matrix having at least one structure selected from a spherical structure, a spiral structure in which a plurality of spherical structures are connected (e.g., coupled) to each
  • the lithium transition metal oxide and the composite are mechanically milled.
  • a Nobilta TM mixer Hosokawa Micron Ltd.
  • the number of revolutions of the mixer during the milling is, for example, about 1000 rpm to about 2500 rpm.
  • the milling speed is less than 1000 rpm, the shear force applied to the lithium transition metal oxide and the composite is weak, so it is difficult for the lithium transition metal oxide and the composite to form a chemical bond.
  • the milling speed is too high, the composite may not be uniformly applied on the lithium transition metal oxide because a formation of the composite is performed in an excessively short time, so it may be difficult to form a uniform and continuous shell.
  • the milling time is, for example, about 5 minutes to about 100 minutes, about 5 minutes to about 60 minutes, or about 5 minutes to about 30 minutes.
  • the content of the composite may be about 3wt% or less, about 2wt% or less, or about 1wt% or less, based on the total weight of the lithium transition metal oxide and the composite.
  • the content of the composite may be about 0.01 parts by weight to about 3 parts by weight, about 0.1 parts by weight to about 3 parts by weight, about 0.1 parts by weight to about 2 parts by weight, or about 0.1 parts by weight to about 1 part by weight based on 100 parts by weight of a mixture of the lithium transition metal oxide and the composite.
  • the average particle diameter (D50) of the composite used in the mechanical milling of the lithium transition metal oxide and the composite is, for example, about 1 ⁇ m to about 20 ⁇ m, about 3 ⁇ m to about 15 ⁇ m, or about 5 ⁇ m to about 10 ⁇ m.
  • Al 2 O 3 particles (average particle diameter: about 15 nm) were introduced into a reactor, and then the temperature in the reactor was increased to 1000 °C under the condition that CH 4 was supplied into the reactor at about 300 sccm and about 1 atm for about 30 minutes.
  • the content of alumina included in the composite was 60 wt%.
  • SiO 2 particles (average particle diameter: about 15 nm) were introduced into a reactor, and then the temperature in the reactor was increased to 1000 °C under the condition that CH 4 was supplied into the reactor at about 300 sccm and about 1 atm for about 30 minutes.
  • Example 1 0.1 wt% of Al 2 O 3 @Gr composite-coated NCA91 (0.06 wt% of alumina)
  • NCA91 LiNi 0.91 Co 0.05 Al 0.04 O 2
  • NCA91 LiNi 0.91 Co 0.05 Al 0.04 O 2
  • Nobilta TM mixer Hosokawa, Japan
  • the mixing weight ratio of NCA91 and the composite prepared in Preparation Example 1 was 99.9:0.1.
  • Example 2 0.25 wt% of Al 2 O 3 @Gr composite-coated NCA91 (0.15 wt% of alumina)
  • a composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing weight ratio of NCA91 and the composite prepared in Preparation Example 1 was changed to 99.75:0.25.
  • Example 3 0.4 wt% of Al 2 O 3 @Gr composite-coated NCA91 (0.24 wt% of alumina)
  • a composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing weight ratio of NCA91 and the composite prepared in Preparation Example 1 was changed to 99.6:0.4.
  • Example 4 1.0 wt% of Al 2 O 3 @Gr composite-coated NCA91 (0.6 wt% of alumina)
  • a composite cathode active material was prepared in substantially the same manner as in Example 1, except that the mixing weight ratio of NCA91 and the composite prepared in Preparation Example 1 was changed to 99.0:1.0.
  • NCA91 was used as a cathode active material.
  • Comparative Example 2 0.4 wt% of SiO 2 @Gr composite-coated NCA91 (0.24 wt% of silica)
  • a composite cathode active material was prepared in substantially the same manner as in Example 3, except that the SiO 2 @Gr composite prepared in Comparative Preparation Example 1 was used instead of the Al 2 O 3 @Gr composite prepared in Preparation Example 1.
  • NMP N-methylpyrrolidone
  • the slurry was applied on an aluminum current collector having a thickness of 15 ⁇ m by bar coating, dried at room temperature, further dried in vacuum, and rolled and punched to obtain a cathode plate having a thickness of 55 ⁇ m.
  • Each coin cell was manufactured using the obtained cathode plate, where lithium metal was used as a counter electrode and a solution in which a PTFE separator and 1.3M LiPF 6 are dissolved in EC (ethylene carbonate) + EMC (ethyl methyl carbonate) + DMC (dimethyl carbonate) (3:4:3 by volume) was used as an electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • XPS spectra were measured using Quantum 2000 (Physical Electronics, Inc.) over time. Before heating, XPS spectra of C 1s orbitals and Al 2p orbitals of samples were measured after 1 minute, after 5 minutes, after 30 minutes, after 1 hour, and after 4 hours, respectively. At the initial heating, only the peak for the Al 2p orbital appeared, and the peak for the C 1s orbital did not appear. After 30 minutes, the peak for the C 1s orbital appeared clearly, and the size of the peak for the Al 2p orbital was significantly reduced.
  • the average contents of carbon and aluminum were measured through XPS analysis results in 10 regions of the composite sample prepared in Preparation Example 1. With respect to the measurement results, a deviation of the aluminum content for each region was calculated. The deviation of the aluminum content was expressed as a percentage of the average value, and this percentage was referred to as uniformity. The percentage of the average value of the deviation of the aluminum content, that is, the uniformity of the aluminum content was 1 %. Therefore, it was found that alumina was uniformly (e.g., substantially uniformly) distributed in the composite prepared in Preparation Example 1.
  • the composite prepared in Preparation Example 1, the composite cathode active material prepared in Example 3, and the bare NCA91 of Comparative Example 1 were subjected to scanning electron microscope (SEM) analysis, high-resolution transmission electron microscope (HR-TEM) analysis, and EDX analysis.
  • SEM scanning electron microscope
  • HR-TEM high-resolution transmission electron microscope
  • EDX EDX analysis
  • FEI's Titan 80-300 was used.
  • the composite prepared in Preparation Example 1 shows a structure in which Al 2 O 3 particles and Al 2 O z (0 ⁇ z ⁇ 3) particles, which are reduction products thereof, are embedded in graphene. It was found that the graphene layer was disposed on the outside of one or more particles selected from Al 2 O 3 particles and Al 2 O z (0 ⁇ z ⁇ 3). One or more particles selected from Al 2 O 3 particles and Al 2 O z (0 ⁇ z ⁇ 3) were uniformly (e.g., substantially uniformly) distributed. At least one selected from Al 2 O 3 particles and Al 2 O z (0 ⁇ z ⁇ 3) has a particle diameter of about 15 nm. The particle diameter of the composite prepared in Preparation Example 1 was about 100 nm to about 200 nm.
  • the composite prepared in Preparation Example 1 shows a D band peak at 1338.7 cm-1 and a G band peak at 1575.0 cm-1 due to graphene.
  • the D band peak is shifted to 1351.3 cm -1 by about 12 cm -1
  • the G band peak is shifted to 1593.6 cm -1 by about 18 cm -1 , due to the shell containing graphene.
  • the shift of the D-band peak was determined to be due to the strain of graphene, which is bonded to the core by milling to form a shell.
  • the shift of the G-band peak was determined to be due to the charge transfer between the core and the graphene in the composite formed by the C-O-Ni bond between the core and the graphene.
  • Each of the lithium batteries manufactured in Examples 5 to 8 and Comparative Examples 3 to 4 was charged with a constant current of 0.1 C rate at 25° C until a voltage reached 4.4 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.1 C rate until the voltage reached 2.8 V (vs. Li) (formation cycle).
  • Each of the lithium batteries having undergone the formation cycle was charged with a constant current of 0.2 C rate at 25° C until a voltage reached 4.4 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 0.2 C rate until the voltage reached 2.8 V (vs. Li) (1 st cycle).
  • Each of the lithium batteries having undergone the 1 st cycle was charged with a constant current of 1 C rate at 25° C until a voltage reached 4.4 V (vs. Li), and was then cut-off at a current of 0.05 C rate while maintaining the voltage at 4.4 V in a constant voltage mode. Subsequently, each of the lithium batteries was discharged at a constant current of 1 C rate until the voltage reached 2.8 V (vs. Li) (2 nd cycle). This cycle was repeated (50 repetitions) until the 50th cycle under the same conditions.
  • Table 1 Initial capacity 0.2C DCH [mAh/g] Capacity retention rate at room temperature [%] Capacity retention rate at high temperature [%]
  • Example 5 Al 2 O 3 @Gr composite 0.1 wt% coating / NCA91 core 207.2 95.2 88.9
  • Example 6 Al 2 O 3 @Gr composite 0.25 wt% coating / NCA91 core 207.5 97.8 92.4
  • Example 7 Al 2 O 3 @Gr composite 0.4 wt% coating / NCA91 core 207.2 98.0 93.2
  • Example 8 Al 2 O 3 @Gr composite 1.0 wt% coating / NCA91 core 205.7 98.0 93.0 Comparative Example 3: Bare NCA91 (no coating) 207.0 93.4 85.7 Comparative Example 4: SiO 2 @Gr composite 0.4wt% coating / NCA91 core 207.2 96.0 89.2
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.25 V, was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.25 V, was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • the discharge capacity in the 3 rd cycle was regarded as standard capacity.
  • each of the lithium batteries was charged to 4.25 V at a rate of 0.5 C, and was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C. Then, each of the charged lithium batteries was stored in an oven at 60 °C for 70 days, was taken out of the oven, and was discharged to 2.8 V at a rate of 0.1 C.
  • Example 5 Al 2 O 3 @Gr composite 0.1 wt% coating / NCA91 core 82.0
  • Example 6 Al 2 O 3 @Gr composite 0.25 wt% coating / NCA91 core 88.6
  • Example 7 Al 2 O 3 @Gr composite 0.4 wt% coating / NCA91 core 89.0 Comparative Example 3: Bare NCA91 (no coating) 65.1
  • Evaluation Example 8 stability test at high temperature of 60 °C (metal elution)
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.25 V, was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.25 V, was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • each of the lithium batteries was charged to 4.25 V with a constant current at a rate of 0.5 C, and was charged with a constant voltage while maintaining the voltage at 4.25 V until a current reached 0.05 C. Then, each of the charged lithium batteries was decomposed to separate a cathode, and then the cathode was immersed into the electrolyte used in manufacturing the lithium battery and stored in an oven at 60 °C for 30 days. Then, the content of metal ions eluted in the electrolyte was measured, and some of the results thereof are shown in Table 3 below.
  • Evaluation Example 9 Evaluation of gas generation amount at high temperature of 80 °C
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.3 V, was charged with a constant voltage while maintaining the voltage at 4.3 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • each of the lithium batteries was charged with a constant current at a rate of 0.5 C until a voltage reached 4.3 V, was charged with a constant voltage while maintaining the voltage at 4.3 V until a current reached 0.05 C, and was discharged at a constant current at a rate of 0.2 C until the voltage reached 2.8 V.
  • each of the lithium batteries was charged to 4.3 V with a constant current at a rate of 0.5 C, and was charged with a constant voltage while maintaining the voltage at 4.3 V until a current reached 0.05 C. Then, each of the charged lithium batteries was stored in an oven at 60 °C for 14 days, was taken out of the oven and put into a jig to be burst, and then the amount of gas generated was measured by converting a change in internal gas pressure into volume. The gas generation amount is expressed as the amount of gas generated per unit weight of the cathode active material included in the lithium battery.
  • a composite cathode active material includes a shell including a first metal oxide and carbonaceous material, cycle characteristics and high-temperature stability of a lithium battery are improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP21177241.3A 2020-06-01 2021-06-01 Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé Active EP3923380B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020200066016A KR102633758B1 (ko) 2020-06-01 2020-06-01 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법

Publications (2)

Publication Number Publication Date
EP3923380A1 true EP3923380A1 (fr) 2021-12-15
EP3923380B1 EP3923380B1 (fr) 2026-04-29

Family

ID=76250124

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21177241.3A Active EP3923380B1 (fr) 2020-06-01 2021-06-01 Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé

Country Status (5)

Country Link
US (1) US20210376314A1 (fr)
EP (1) EP3923380B1 (fr)
JP (1) JP7348231B2 (fr)
KR (1) KR102633758B1 (fr)
CN (1) CN113764665B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118841560A (zh) * 2024-09-20 2024-10-25 赣州诺威科技有限公司 双包覆改性钠离子电池正极材料及其制备方法、钠离子电池
EP4307407A4 (fr) * 2021-03-10 2025-03-26 Samsung SDI Co., Ltd. Matériau actif de cathode composite, cathode et batterie au lithium l'utilisant, et son procédé de fabrication

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102426254B1 (ko) * 2019-03-28 2022-07-28 삼성에스디아이 주식회사 리튬 이차전지용 전해질 첨가제를 포함하는 리튬 이차전지
EP4216307A4 (fr) * 2020-12-22 2024-10-16 LG Energy Solution, Ltd. Procédé de fabrication d'électrode positive pour batterie rechargeable au lithium et électrode positive pour batterie rechargeable au lithium ainsi fabriquée
KR20220136752A (ko) * 2021-04-01 2022-10-11 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법
CN114824271B (zh) * 2022-04-13 2024-04-26 中国计量大学 一种阳极材料及其制备方法、锂电池阳极及其制备方法、锂电池
WO2024025104A1 (fr) * 2022-07-28 2024-02-01 주식회사 엘지에너지솔루션 Matière de cathode pour batterie au lithium-soufre et batterie au lithium-soufre la comprenant
KR102820708B1 (ko) * 2022-08-19 2025-06-12 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
KR20240044922A (ko) * 2022-09-29 2024-04-05 삼성에스디아이 주식회사 양극 및 이를 포함하는 전고체 이차전지
KR20240044921A (ko) * 2022-09-29 2024-04-05 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 이의 제조방법
WO2024096619A1 (fr) * 2022-11-04 2024-05-10 삼성에스디아이주식회사 Matériau actif de cathode composite, son procédé de préparation, et cathode et batterie secondaire entièrement solide comprenant chacun celui-ci
KR102873761B1 (ko) * 2022-12-14 2025-10-17 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 이의 제조방법
KR20240096151A (ko) * 2022-12-19 2024-06-26 삼성에스디아이 주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법
KR20240103831A (ko) * 2022-12-27 2024-07-04 삼성에스디아이 주식회사 건식 전극 필름, 이를 포함하는 건식 전극 및 리튬전지
CN116093309B (zh) * 2023-03-07 2023-06-20 中南大学 一种锑改性的高镍三元层状复合正极材料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100310940A1 (en) * 2008-11-10 2010-12-09 Daejung Em Co., Ltd. Cathode active material for lithium secondary batteries with high safety, method of preparing the same and lithium secondary batteries comprising the same
US20140377655A1 (en) * 2013-06-24 2014-12-25 Samsung Electronics Co., Ltd. Composite cathode active material, method of preparing the composite cathode active material, and cathode and lithium battery each including the composite cathode active material
US20150037680A1 (en) * 2013-07-31 2015-02-05 Samsung Electronics Co., Ltd. Composite cathode active material, lithium battery including the same, and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030138697A1 (en) * 2002-01-24 2003-07-24 Randolph Leising Cathode active material coated with a metal oxide for incorporation into a lithium electrochemical cell
US8257867B2 (en) * 2008-07-28 2012-09-04 Battelle Memorial Institute Nanocomposite of graphene and metal oxide materials
WO2010079963A2 (fr) * 2009-01-06 2010-07-15 주식회사 엘지화학 Matériau actif d'électrode positive et batterie rechargeable au lithium comprenant ce matériau
CN102237515B (zh) * 2010-04-20 2016-01-06 深圳市比克电池有限公司 锂离子电池、正极活性材料及其制备方法
JP2012169217A (ja) * 2011-02-16 2012-09-06 Asahi Glass Co Ltd リチウムイオン二次電池用の正極活物質およびその製造方法
US9460827B2 (en) * 2011-11-07 2016-10-04 Dhkgraphenologies Llc Physically functionalized graphene hybrid composite (GHC) and its applications
KR101465490B1 (ko) * 2011-11-30 2014-11-26 주식회사 코캄 안전성과 안정성이 향상된 리튬 이차 전지
EP2816639A3 (fr) * 2013-06-19 2015-05-13 QuantumScape Corporation Revêtements protecteurs pour cathodes de matériau de conversion
JP2015170476A (ja) * 2014-03-06 2015-09-28 トヨタ自動車株式会社 リチウムイオン二次電池の製造方法
SG11201609456YA (en) * 2014-05-14 2016-12-29 Agency Science Tech & Res A method of forming a porous particle
CN107004918A (zh) * 2014-08-27 2017-08-01 尼沃系统公司 锂金属氧化物复合材料及其制备和使用方法
EP3323164A4 (fr) * 2015-07-13 2019-01-09 Sila Nanotechnologies Inc. Cathodes stables à base de fluorure de lithium pour batteries métal et métal-ion
CN106450270B (zh) * 2015-08-13 2020-08-11 中国科学院物理研究所 锂离子二次电池的正极活性材料及其制备方法和应用
EP3363066A4 (fr) * 2015-10-14 2019-03-27 Northwestern University Cathodes de spinelle d'oxyde métallique revêtues de graphène
JP2017103207A (ja) * 2015-11-19 2017-06-08 Tdk株式会社 正極活物質、正極、及びリチウムイオン二次電池
CN108370060B (zh) * 2015-12-15 2023-06-30 新罗纳米技术有限公司 用于安全金属和金属离子电池的固态电解质
CN116565296A (zh) * 2016-07-05 2023-08-08 株式会社半导体能源研究所 锂离子二次电池
CN110140244A (zh) * 2017-01-06 2019-08-16 沙特基础工业全球技术公司 含有多硫化物捕获剂的蛋黄-壳结构、其制备方法及其用途
KR102629462B1 (ko) * 2018-10-04 2024-01-26 삼성전자주식회사 복합양극활물질, 이를 채용한 양극과 리튬전지 및 그 제조방법
KR102797282B1 (ko) * 2018-12-21 2025-04-21 에이일이삼 시스템즈 엘엘씨 사전 리튬화 코팅을 갖는 캐소드 및 조제 및 사용 방법
US11735710B2 (en) * 2019-05-21 2023-08-22 Uchicago Argonne, Llc Cathode materials for secondary batteries
CN111082046B (zh) * 2019-12-31 2021-07-16 中科廊坊过程工程研究院 一种包覆型正极材料及其制备方法和用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100310940A1 (en) * 2008-11-10 2010-12-09 Daejung Em Co., Ltd. Cathode active material for lithium secondary batteries with high safety, method of preparing the same and lithium secondary batteries comprising the same
US20140377655A1 (en) * 2013-06-24 2014-12-25 Samsung Electronics Co., Ltd. Composite cathode active material, method of preparing the composite cathode active material, and cathode and lithium battery each including the composite cathode active material
US20150037680A1 (en) * 2013-07-31 2015-02-05 Samsung Electronics Co., Ltd. Composite cathode active material, lithium battery including the same, and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DOU SHUMEI: "Review and prospect of layered lithium nickel manganese oxide as cathode materials for Li-ion batteries", vol. 17, no. 4, 1 April 2013 (2013-04-01), DE, pages 911 - 926, XP055843229, ISSN: 1432-8488, Retrieved from the Internet <URL:https://link.springer.com/content/pdf/10.1007/s10008-012-1977-z.pdf> DOI: 10.1007/s10008-012-1977-z *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4307407A4 (fr) * 2021-03-10 2025-03-26 Samsung SDI Co., Ltd. Matériau actif de cathode composite, cathode et batterie au lithium l'utilisant, et son procédé de fabrication
CN118841560A (zh) * 2024-09-20 2024-10-25 赣州诺威科技有限公司 双包覆改性钠离子电池正极材料及其制备方法、钠离子电池

Also Published As

Publication number Publication date
CN113764665A (zh) 2021-12-07
JP7348231B2 (ja) 2023-09-20
KR102633758B1 (ko) 2024-02-05
EP3923380B1 (fr) 2026-04-29
US20210376314A1 (en) 2021-12-02
KR20210148741A (ko) 2021-12-08
CN113764665B (zh) 2024-10-18
JP2021190431A (ja) 2021-12-13

Similar Documents

Publication Publication Date Title
EP3923380B1 (fr) Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé
CN108075115B (zh) 复合正极活性材料、包含其的正极和锂电池、以及制备复合正极活性材料的方法
US10763503B2 (en) Composite cathode active material, cathode and lithium battery including the composite cathode active material, and method of preparing the composite cathode active material
EP3923379B1 (fr) Matériau actif de cathode composite, cathode le comprenant, batterie au lithium utilisant la cathode et procédé de préparation associé
US12580180B2 (en) Composite cathode active material, cathode and lithium battery containing composite cathode active material and preparation method thereof
JP7342162B2 (ja) 正極、それを採用したリチウム電池、及びその製造方法
KR20150017012A (ko) 복합 양극 활물질, 이를 포함하는 리튬 전지, 및 이의 제조방법
US20230268485A1 (en) Composite cathode active material, cathode and lithium battery which employ same, and preparation method therefor
EP4307407A1 (fr) Matériau actif de cathode composite, cathode et batterie au lithium l&#39;utilisant, et son procédé de fabrication
EP3467913A1 (fr) Matière active d&#39;électrode négative, matière active d&#39;électrode négative mixte et procédé de production d&#39;une matière active d&#39;électrode négative
EP4318652A1 (fr) Matériau actif de cathode composite, cathode et batterie au lithium utilisant celui-ci, et son procédé de préparation
KR20220169559A (ko) 음극 활물질, 그의 제조방법 및 이를 포함하는 리튬 이차전지
EP4186858A1 (fr) Composite poreux, anode et batterie au lithium comprenant chacune celui-ci, et méthode de préparation associée
KR20230000615A (ko) 음극 활물질, 그의 제조방법 및 이를 포함하는 리튬 이차전지

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210601

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

B565 Issuance of search results under rule 164(2) epc

Effective date: 20211115

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20260121

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: F10

Free format text: ST27 STATUS EVENT CODE: U-0-0-F10-F00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260429